Photographic printout methods and materials utilizing organic azide compounds and coupler compounds therefor



United States Patent 3,282,693 PHOTOGRAPI-IIC PRINTOUT METHODS AND MA- TERIALS UTILIZING ORGANIC AZIDE COM- lgIRTNDS AND COUPLER COMPOUNDS THERE- John J. Sagura and James A. Van Allan, Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N .Y., a corporation of New Jersey No Drawing. Filed Oct. 1, 1962, Ser. No. 227,561 17 Claims. (CI. 96-49) This application is a continuation-impart of abandoned US. patent application Serial No. 6,888 filed February 5, 1960.

This invention relates to photographic reproduction methods and materials and particularly to photographic print-out system comprising certain organic azides in combination with certain nitrogen containing heterocyclic compounds hereinafter referred to as 'heterocyclic couplers.

Various organic azido compounds are known to be ligtht sensitive and have been previously employed in photographic applications. For example, certain light sensitive azido compounds have been incorporated in layers of albumin, starch and the like in which they act to harden or tan the colloid under the influence of light. The untanned areas of the colloid layer are then dissolved away to produce an image useful in photomechanical reproduction methods. British Patent 765,909, published January 16, 1957, also describes colloid-free printing plates coated with certain light sensitive azido benzirnidazoles. Unexposed areas of the light-sensitive layers on these plates can be removed by treatment with a dilute alkaline solution. The plates may then be washed and the relief image swabbed with a greasy ink for printing purposes.

It is an object of the present invention to provide photographic reproduction methods and materials employing lighthensitive compositions comprising azides in combination with certain heterocyclic couplers ca pable of yielding print-out images on exposure to light.

It is another object of the invention to provide an azidehetenocyclic coupler sensitized photographic print-out material having improved contrast between the image and non-image areas of the print.

A further object of the invention is to provide a photographic print-out material comprising a unitary layer serving both as the support and as the light sensitive layer of the material.

These and other objects of the invention, which will become apparent from the detailed description below, are attained by providing a photographic element comprising either a conventional photographic support coated with a colloid layer in which; certain light sensitive. organic azido compounds and certain heterocyclic couplers are dissolved or dispersed or a similar photographic material in which the azido compounds and heterocyclic couplers are incorporated in a self-supporting layer. Photographic elements of this type, including films, plates, photographic printing papers, copying papers and the like, when sensitized with the azide-heterocyclic coupler compositions of the present invention and given an im-agewise exposure to actinic light produce the desired print-out images.

Although we have discovered that many organic azido compounds react with a wide variety of nitrogen-containing heterocyclic compounds, only certain of these azido compounds are useful in the present invention since the others react too slowly for photographic purposes or do not form compounds sufliciently highly colored to provide the desired contrast in the print-out image.

The organic azido compounds useful in the present invention have the general formulae:

wherein Ar represents an aryl group (e.g. phenyl, a-naph thyl, B-naphthyl, and aryl gnoups substituted with any of the nucleophilic and electnophilic groups, for example, 4-methoxyphenyl, 3-ethylphenyl, 2-propylphenyl, 2- chlorophenyl, 3-fluorophenyl, 4-nitrophenyl, Z-hydroxyphenyl, 3-hydroxyphenyl, Z-aminophenyl, 4-phenoxyphenyl, 4-phenylthiophenyl, 4-azidophenylthio-4-phenyl, 7-Stilb8ZO16, 9-acridine, 2-methoxy-7-chloro-9-acridine, ahydroxy-Bmaphthyl, fl-hydroxy oz naphthyl, etc.); Q represents a group selected from the class consisting of the oxygen atom, the sulfur atom, the selenium atom, a NR group, etc.; R represents a group selected from the class consisting of the hydrogen atom, an alkyl group (e.g. methyl, ethyl, propyl, butyl, etc.), an aryl group (e.g. phenyl -4-methylphenyl, 3-ethylphenyl, 2-methoxyphenyl, 4-ethoxyphenyl, 4-nitrophenyl, Z-nitrophenyl, etc.), a substituted sulfonyl group (e.g. methylsulfonyl, phenethylsu-lfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, phenylsulfonyl, p-tolylsulfonyl, m-tolylsulfonyl, etc), an alhoyl group (eg actyl, trichloroacetyl, trifluoroacetyl, propionyl, 'butryl, etc.), an anoyl group (e.g. benzoyl, naphthoyl, etc), a carbalkoxy group (e.g. carbethoxy, carbomethoxy, carbopropoxy, etc), a carbamyl group (e.=g. carbamyl, methylcarbamyl, propylcarbamyl, butylcarbamyl, hexylcarbamy-l, octylcarbamyl, dodecylcarbamyl, carb omethoxymethylcarb amyl, carbethoxymethylcarbamyl, carbobutoxymethylcarbamyl, carbopropoxyme-thylcarbamyl, carbethoxypropylcarbamyl, carbethoxybutylcarbamyl, carbethoxyhexylcanbamyl, carbethoxyoctylcar-bamyl, carbethoxyundecylcarbamyl, carbethoxydodecylcarbamyl, phenylcarbamyl, a-naphthylcarbamyl, a-carbamyldiethylsuccinato, a-carbamyldiethylglutar-ato, etc.); R and R each represents a group selected from the class consisting of the hydrogen atom, an alkyl group (e.g. methyl, ethyl, phenethyl, propyl, Z-hydroxyethyl, butyl, etc.), an alkoxy group (e.g. methoxy, ethoxy, propoxy, butoxy, phenethoxy, etc.), an aryl group (e.g. phenyl, tolyl, etc.), the nitro group, halogen atom (e.g. chlorine, bromine, fluorine, etc.), and the non-metallic atoms such that when R and R are attached to adjacent carbon atoms in the benzene ring and the said nonmetallic atoms of the R and R taken together with the said carbon atoms complete a fused cyclic ring (e.g. phenyl); R represents .a group selected from the class consisting of the azido grouup, and an alkyl group (e.g. methyl, ethyl, propyl, etc.) R represents a group selected from the class consisting of the azido group, an alkyl group (e.g. methyl, ethyl, propyl, etc.), an amino group (e.g. amino, N-phenylamino, N-methylamino, N propylamino, etc.); Z represents a member selected from the class consisting of the =CH group and the nitrogen atom; and R represents a member selected from the class consisting of the hydrogen atom, and an alkyl group (e.g. methyl, ethyl, phenethyl, propyl, etc.).

Specific azides useful in the invention include:

Name of Azide (e.g. methyl, ethyl, propyl, etc.), an aryl group (e.g. phenyl, tolyl, naphthyl, etc.), etc.; R and R each represents a group selected from the class consisting of the hydrogen atom, an alkyl group (e.g. methyl, ethyl, phenethyl, 2-hydroxyethyl, propyl, butyl, etc.), an alkoxy group (e.g. methoxy, ethoxy, propoxy, butoxy, phenethoxy, etc.), an aryl group (e.g. phenyl, tolyl, etc.), the nitro group, a halogen atom (e.g. chlorine, bromine, fluorine, etc.), and the non-metallic atoms such that when the R and R groups are taken together with adjacent carbon atoms in the benzene ring (to which they are attached) they form a fused carbocyclic ring (e.g. phenyl) or a fused heterocyclic ring; R and R each represents a group selected from the class consisting of the hydrogen atom, an alkyl group (e.g. methyl, ethyl, phenethyl, propyl, butyl, etc.), an alkoxy group (e.g. methoxy, ethoxy, propoxy, butoxy, phenethoxy, etc.), an aryl group (e.g. phenyl, tolyl, etc.), the nitro group, a halogen atom (e.g. chlorine, bromine, fluorine, etc.), the hydroxy group, the oxygen atom, etc. and the non-metallic atoms such that when the R and R groups are taken together with adjacent carbon atoms in the benzene ring (to which they are attached) they form a fused carbocyclic ring (e.g. phenyl) or a fused heterocyclic ring; W represents a group selected from the class consisting of the sulfur atom, the selenium atom, the oxygen atom, the

es -?X group, the IIT groupand the CH group, R represents an alkyl group (e.g. methyl, ethyl, etc.); X represents an acid anion (e.g. chloride, bromide, iodide, chlorate, p-toluenesulfonate, thiocyanate, etc.); R represents a group selected from the class consisting of the hydrogen atom, an alkyl group (e.g. methyl, ethyl, propyl, etc.), such that at least one position ortho or one position para to the imino group of the coupler compound is unsubstituted (that is has only a hydrogen atom); and n represents an integer of COUPLER Name Phenothiazine. 3-nitrophenothiazine. l-methoxyphenothiazine. l-hydroxyphenothiazine. 3-isopropoxyphenothiazinev 3,G-dimethylphenothiazine. Dihydrobenzothiazine. S-methylphenothiazine. Benzo[a]phenothiazine. 9-methoxybenzo[a]phenothiazine. Benzo[b]phenothiazine. 6,1l-dioxobenzo[b]phen0thiazine.

The heterocyclic coupler compounds used to advantage according to our invention include those represented by the formulae:

wherein R and R each represents a group selected from the class consisting of the hydrogen atom, an alkyl group 1,6-dimethoxybenz0[b]phen0thiazine. Benzo[c]phenothiazine. Dibenzo[a,j]phenothiazine. Dibenz0[a,h]phenothiazine. Benzo[a]phenoselenazine.

Phenoxazine.

Benzo[c]phenoxazi.ne. Benzo[b]phenoxazine.

Dimer of benzo[b]phenoxazine. 9-methylbenzo[b]phenoxazine.

Dimer of Q-methylbenzo[b]phen0xazine. Q-t-butylbenzo[b]phenoxazine.

Dimer of 9-t butylbenzo[b]phenoxazine. Aeridan.

- S-hydroxyacrldan.

N-methyldihydrophenazine.

Substituents on the aryl ringsof the heterocyclic couplers have been observed to greatly afiect the rate with which the heterocyclic couplers couple with the azide irradiation products.

The azides represented by the second and third formulae above, i.e., th'e aroyl azides and their vinylogs, are generally less active than the other azides for the purpose of the present invention unless a third substance,

a salt of a basic ammonia derivative, is added to the azide-heterocyclic coupler composition. The identity of the salt of a basic ammonia derivative employed to promote the formation of colored compounds by the irradiation of the aroyl azides and their vinylo-gs in the presence of the heterocyclic couplers is not critical. The term basic ammonia derivative is intended to include all basic nitrogen compounds capable of salt forrnation. Although any salt of these compounds may he used, it is preferred for convenience to employ the salts of the strong mineral acids and particularly the hydrochl-orides, sulfates and nitrates. Specific salts which have been found to be useful include ammonium chloride itself and the hydrochlorid'es of, for example, 4-aminodiphenylamine, 3,3'-dimethoxybenzidine, Z-aminobenzothiazole, 1,1'-diphenylhydrazine, poly(aminostyrene), diethylamine, guanidine, 2-aminobiphenyl, p-toluidine, and phenothiazine among others.

The light-sensitive elements of the present invention may be prepared 'by conventional coating procedures. In general, the azides and heterocyclic couplers are dissolved or dispersed in a natural or synthetic polymer in a suitable solvent and coated on a suitable photographic support by means of a plate Whirler or other device capable of producing a thin, uniform coating of the light-sensitive composition. The vehicle in which the light-sensitive composition is coated may be any of the natural or synthetic high polymers ordinarily used for photographic layers, such as gelatin, casein, polystyrene, vinyl resins including poly(vinyl alcohol), poly(vinyl b utal) 'etc., cellulose derivatives, or mixtures of these polymers. The support for the light-sensitive layer may be a plate, sheet or strip of any of the commonly used materials, such as paper, cellulose derivatives, .glass, synth'etic high polymers and the like. Any of the solvents commonly employed in the art for coating high polymer layers may be used with advantage, an excellent solvent for this purpose being Z-butanone.

It is advantageous to add solvents, such as cyclohexanone, cellosolve, benzene, methyl ethyl ketone, ethylene chloride, toluene, methyl isobutyl ketone, cellosolve acetate, etc. which have higher boiling points than the basic solvent used, such as acetone in the preparation of the coating composition. Use of the higher boiling solvent in the amount of about percent of the total mixture by weight has been found to reduce the drying rates of the coatings, thus insuring a more uniform coating that is free of mottle. The addition of solvents, such as benzene and toluene also improves the keeping properties of the coating composition.

In addition to the more conventional procedure of coating the described light sensitive compositions in a colloid layer on an inert photographic support, the invention also includes, in another embodiment, the provision of light-sensitve elements in which the light-sensitive composition is inconporated in the base layer thus eliminating one of the two coating operations usually required. This may be accomplished by dissolving the aztide, the heterocyclic coupler, and a high polymer such as cellulose triacetate in a suitable organic solvent such as a mixture of methylene chloride and methanoland coating the resulting composition on a glass plate or other suitable surface. When the coating has dried sufliciently it is stripped from the glass plate to produce a self-supporting film containing the light sen-sitive azide-heterocyclic couple-r composition. Similarly, .any of the high polymers, natural or synthetic, such as those mentioned :above, that can be cast into clear flexible films, can be used in place of cellulose triacetate to make self-supporting light sensitive elements.

The light-sensitive 'elements of the invention, whether of the type in which the azide-heterocyclic coupler composition is coated in a colloid layer on a separate support or of the type in which the base itself contains the light sensitive composition, produce a colored print-out image on an uncolored background when exposed through .a pattern to a suitable source of .actinic light. The lightsensitive layer becomes colored where it is exposed to light and thus a positive print-out imag'e will be obtained when the exposure is made through a negative or a negative image when the exposure is made through a positive. Any suitable suorce of actinic light may be employed for the exposure including an lamps, mercury lamps, photofiood lamps and sun lamps.

Specific embodiments of the invention will now be described in greater detail in the following illustrative examples.

Example I A coating solution consisting of 50 grams of a 10% dope of Vinylite VYLF in 2-butanone, 1.0 gram or 2- tazido-1phenylcarbamylbenzimidazole land 0.3 gram of benzo[b]|phenoxazine was coated onto a paper support and dried. The resulting light-sensitive photographic element was exposed through 'a continuous-tone negative by means of an R.S. sunlamp to produce a nearly neutral positive print-out image. Vinylite VYLF is a copolymer of vinyl chloride and vinyl acetate, -88% vinyl chloride, molecular weight 6,000.

Example 2 Twenty grams of 2-az-ido-l-carbobutoxymethylcarbamylbenzimidazole and 1.0 gram of benzo[b]phenoxazine were dissolved :in 600 grams of a 10% dope of cellulose acetate propionate polymer in Z-butanone. This solution was coated onto a paper support and exposed as in Example 1 to produce a blue-black image.

Example 3 A coating solution was prepared by dissolving 0.3 gram of 2-azido 1 car-bobu-toxymethylcarbamylbenzimidazole and 0.1 gram of aoridan in 25 grams of 10% Vinylite VYLF in Z-butanone. This coating When exposed to a source of ultraviolet radiation produced a purple printout image.

Example 4 A coating solution was prepared by dissolving 0.3 gram of 2-rnethoxy-6-chloro-9-azidoacridine and 0.2 gram of ph'enothiazine in 25 grams of 10% Vinylite VYLF in 2- butanone. When this composition was coated on a photographic support and exposed to a .source of ultraviolet radiation, a red-brown print-out image was obtained.

Example 5 A coating composition was prepared by dissolving 14 grams of Z-azidobenzoxaz-ole, 1.8 grams of benzo[a]- phenot-hiazine and 0.5 gram of 4-quinolizone in 150 grams of a vinyl dope in 105 grams of Z-butanone. The vinyl dope was composed of 40% Vinylite VYLF (described above) and 60% Vinylite VYHH, the latter being a copolymer of vinyl chloride and a vinyl acetate containing 8588% of vinyl chloride and having a molecular weight of 10,000. This composition was coated onto a conventional cellulose acetate photographic support and dried to produce a light-sensitive photographic element having a concentration of about 3 grams of solids per square foot. When exposed to an ultraviolet-rich light source through a photographic negative a positive print-out image was obtained. This image was stabilized by heating the photographic element to a temperature of about -100" C. for a short period of time.

Example 6 A solution of 0.4 gram of Z-azidobenzoxazole and 0.25 gram of phenothiazine in 25 grams of a benzene dope containing 1% by weight of crepe rubber and 5% by Weight ofi polystyrene was Whirl-coated onto a paper support and allowed to dry. The resulting coating was ex.- posed for 30 seconds to a s-unlamp at 'a distance of 10 inches through a negative pattern to produce a blue-on- 7 white positive image. This print was stabilized by heating at 100-430 C. for 20 seconds.

Example 7 A solution of 0.3 gram of 1ca-rboethoxymethyl-3-(2- azidobenzi'midazole-l )urea and 0.1 gram of phenothiazine in 25 grams of benzene dope containing 1% by weight of crepe rubber and 5% by weight polystyrene was whirlcoated on a paper support. The dry coating was exposed for 30 seconds to a sunlamp at inches through a negative pattern to obtain a blue-on-white positive image.

Example 8 To 40 ml. of a 10% solution of Viny-lite VYLF in 2- b uta-n-one was added 0.176 gram of 2,4-diazid-o-6-methylpyrimidine and 0.4 gram of phenothiazin-e and the mixture was shaken to effect solution. The resulting solution was coated on paper by means of a plate whirler and the plate whirled until dry. The coated side of the paper plate was exposed through a negative pattern for 30 seconds to a sun-lamp at a distance of 10 inches to produce a sepi'aon-white positive print. This print was stabilized by heating 100130 C. for 20 seconds.

Example 9 To 50 ml. of a 10% solution of Vinylite VYLF in 2- butanone was added 0.1 gram of 2,4,6-triazido-sym-triazine, 0.3 gram of phenothiazine and 5 drops of dimethyl sulfoxide. The resulting mixture was shaken to effect solution and then coated on a paper support as in Example 8. The dry paper plate was exposed through a negative pattern for 30 seconds to a sunlamp at 10 inches to produce a sepia-on-wh-ite positive print.

Example 10 A coating solution was prepared by dissolving 0.1 gram of 5-azid-otetrazole[-a]phthalazine and 0.2 gram of phenothiazine in 100 ml. of a 10% Vinylite VYLF-2-butan0ne solution. This solution was coated on a paper support by means of a plate whirler and whirled until dry. The resulting light-sensitive plate was exposed through a negative pattern for 1 minute to a sunlamp at a distance of 10 inches to produce a vi-oleton-white positive print.

Example 11 A 10% Vinyli-te VYLF solution in Z-butanone containing 0.1 gram of phenoth-i'azine and 0.13 gram of 4,4- diazidodiphenyl sulfide was coated on paper by means of a plate whirler. The dry plate was exposed through a negative to a sun-lamp at 10 inches for 1 minute to obtain a violet-on-white positive image.

Example 12 A 5% by weight solution of polyvinylbutal in methanol was saturated with Z-aminobiphenyl hydrochloride. Equivalent amounts of phenothiazine and 'benz-oyl azide were added. The resulting solution was coated on :paper by means of a plate whirler and the plate whirled until dry. The dry plate was exposed through a negative to a sunlamp at a distance of 10 inches for 1 minute to obtain a red-violet positive print-out image. The plate was then stabilized by washing with warm water for five minutes.

Example 13 A 5% by weight solution of polyvinylbutal in methanol was saturated with aniline hydrochloride. Equivalent amounts of 2,4,G-triazido-sym-triazine and phenqthiazine were added. The resulting solution was coated on paper by means of a plate whirler and the plate whirled until 8 dry. The dry plate was exposed through a negative to a sunlamp at a distance of 10 inches for 1 minute to obtain a blue print-out image of good quality. This procedure was repeated employing a number of other salts of basic ammonia derivaties in place of the aniline hydrochloride. Table I below lists the salts and the color of the print-out images obtained in each case.

It has been observed that the color of the image formed in the embodiments of the invention in which the lightsensitive composition contains an aroyl azide or a vinylog of such an azide, a heterocyclic coupler, and a salt of a basic derivative of ammonia is dependent upon the pH of the stabilized coating. The dye base in this system is apparently red in color while its salts are blue. The color of the print-out image is, therefore, determined by the relative amounts of dye base and dye salt present and thus may range from blue through violet or red-violet as shown in Table I above.

Light-sensitive elements of the invention in which a salt of a basic ammonia derivative is employed to promote dye formation and in which the light-sensitive layer is water-permeable may be stabilized by washing for a few minutes with warm water or a dilute acid in order to remove unreacted salt, prints stabilized in this way may be stored for extended periods of time.

Example 14 A light-sensitive element comprising a composite support and light sensitive layer was prepared by dissolving 5 grams of 1-phenylcarbamido-2-azidobenzimidazole, 1 gram of benz[a]phenothiazine and 20 grams of cellulose triacetate in 162 grams of methylene chloride and 18 grams of methanol and coating the resulting dope on a glass plate to a thickness of 0.035 inch. The coating was dried for 6 hours at room temperature. The film was then stripped from the glass plate and exposed for two minutes to a sunlamp through a step-wedge negative. The visible image was intensified by heating several minutes at 65 C. A maximum density (Dmax) of 3.3 and a minimum density (Dmin) of 0.22 were obtained in the print-out image.

Example 15 To 25 grams of a 10% dope of cellulose acetate propionate in 2-butanone were added 0.5 gram of the azide compound and 0.2 gram of the heterocyclic coupler. After solution was complete, the dope was used to make a coating on paper stock at a coverage of approximately 2 grams per square foot. The dope coating was exposed through a negative to a source of ultraviolet light to effect the print-out. Occasionally, the light-sensitive compounds were incompletely soluble in Z-butanone; in such cases they were dissolved in a benzene or ethylene chloride dope of polystyrene or a methanolic dope of polyvinyl butal and then coated in the usual manner. The images formed are described below.

Azlde Number Heterocyclic Coupler Number Image Color Blue.

Blue. Blue-gray. Green. Orange-brown. Brown.

Blue.

Do. Brown. Neutral. Blue. Orange. Blue Purple. Blue D o Brown. Blue. Orange. Brown. Bluish-gray. Purple.

Do. Reddish-brown. Purple-brown. Red.

Brown. Purple. Do. Orange. Red. Orange. Reddish-brown. Red-orange.

Light green. Des-aturated green. Dark blue.

Gray.

Brown.

Violet.

Do. Dark purple. Magenta. Brown.

Do. Purple.

D0. Cold neutral. Desaturated yellow. Brown.

Do. Faint gray. Warm neutral. Cold neutral.

Do. Warm neutral. Pale cold neutral. Tan. Tan. Neutral. Pale neutral. Orange. Desaturated purple. Cold neutral. Desaturated purple. 'Ian. Tan. Brown.

Do. Red. Brown. Orange.

The ratio of the reactants can be varied considerably although it is generally preferred to employ approximately stoichiometric amounts of the azides and heterocyclic couplers. Any ratio of azide to heterocyclic coupler which will produce a print-out image of the desired contrast may be employed; however, the ratio required for this purpose depends upon the contrast desired, the intensity of color of the compound produced, the color of the background and the particular azide and heterocyclic coupler combination employed.

Mixtures of two or more azide compounds with one or more heterocyclic couplers, or mixtures of one azide compound with two or more heterocyclic couplers are used to advantage in our print-out system. For example, neutral-toned print-out images are desirable in portrait proofing applications. Neutral-toned print-out images are pro duced by using two color image-forming systems which produce colors that combine to form a neutral image. The two color-forming systems should preferably have the same or nearly the same photographic speeds so that the neutral tones will be produced at all levels of image densities. Various variations from neutral tones are produced by either varying the ratios of the two color-forming systems from the neutral tone producing combination, or by using other mixtures of color-forming systems. Representative systems are illustrated by the following examples.

Example 1 6 A coating dope was made consisting of 50 grams of cellulose acetate, 1'7 grams of 2-aZido-1-carbobutoxymethylcarbamylbenzimidazole, 1.5 grams of 2-azido-1- phenylcarbarnylbenzimidazole, 1.0 gram of benzo[b]phenoxazine and 200 grams of acetone. The clear dope was applied to a baryta coated paper stock by means of a hopper coating machine at a coverage of 1.6 grams/ft. (dry solids) and dried. Exposure of this coated product to an ultraviolet source through a negative produced a positive print that was nearly neutral at all density levels.

Example 1 7 To 60-grams of a 10% solution of cellulose acetatepropionate in Z-butanone is added 3 grams of 2-azido-lcarboisobutoxyrnethylcarbamylbenzimidazole, 0.4 gram of 2-azido-l-phenylcarbamylbenzimidazole and 0.25 gram of benzo [b] phenoxazine. Coatings prepared from this composition yielded excellent prints having neutral tones at all density levels.

Example 18 To 25 grams of a 10% solution of vinylite resin (decribed in Example 5) in Z-butanone was added 0.5 gram of 2-azido-1-phenylcarbamylbenzimidazole, 0.2 gram of phenothiazine and 0.2 gram of benzo[c]phenothiazine. This dope was coated by means of a plate-whirler onto a baryta-coated paper stock, dried and exposed to an ultraviolet light source through a continuous tone negative. The resulting print-out color when compared to that obtained from a similar formulation which lacked benzo[c] phenothiazine, exhibited a hue shift toward the green. This composition gave more pleasing prints with certain subjects, such as landscapes and marine scenes.

Example 19 To 25 grams of a 10% solution of Vinylite resin (described in Example 5) in butanone was added 0.2 gram of 2-azido-1-phenylcarbamylbenzimidazole, 0.2 gram of 2-azidobenzoxazole, 0.1 gram of benzo[a]phenothiazine, and 0.1 gram of phenothiazine. Coatings made as in Example 18, produced prints with a violet hue and afiorded a degree of contrast control of wider latitude than was available from the coating of Example 5.

Example 20 To 60 grams of a 10% solution of polystyrene in ethylene chloride was added 1.5 gram of 2-azido-1-phenylzinc, and 0.1 gram of phenothiazine. Coatings made from this formulation yielded a blue print-out image which was less saturated than that obtained when the benzofbjphenoxazine was omitted. This combination affords a better rendition of certain subjects, such as snow scenes and architectural subjects.

It should be noted that certain of the light-sensitive compositions of the presetnt invention are also afiected by heat and this property can be used to advantage. For example, certain of the azides can be inactivated, or removed from the coating by thermal diffusion by heating at temperatures of about 75150 C. for periods ranging from about 10 to 30 seconds or more. This makes it,

possible to stabilize print-out images containing residual unexposed azides of this group merely by heating the print for a short time to a temperature suflicient to inactivate or remove the unreacted azide but not so high as to adversely affect the print itself. Specific azides of this type include the 2-azidobenzoxazole of Examples 5 and 6 and the 2,4-diazido-o-methylpyrimidine of Example 8, which can be, respectively, removed from the coating by thermal diffusion and inactivated by heating at 95l30 C. for about 20 seconds.

With certain other light-sensitive compositions of the invention heat may also be employed to intensify the print-out image obtained by exposure to light. The composition described in Example 14 which contains l-phenylcarbamido-2-azidobenzimidazole and benz[a]phenothiazinc is an example of such a composition.

The print-out images can be stabilized advantageously by treating them with certain solvents which are capable of differentially extracting the residual light-sensitive azide from the photographic layer while leaving the major part of the print-out dye image and not attacking the vehicles. Solvents useful for this purpose at room temperature include methanol, ethanol, butyl acetate, a 4:1 mixture of isopropanol and acetone. Trichloroethylene is used to advantage at elevated temperatures for removing residual azide compound.

As noted previously, the presence or absence of substituents on the reactants and particularly on the aryl rings of the heterocyclic couplers has a profound eifect on the rate or speed with which the coupling reaction occurs. This may be due to an increase in the electron density at the coupling site or because the heterocyclic coupler itself is acting as a sensitizer for the azide. It now seems that the latter is the more important effect since heterocyclic couplers which react fastest with the azide irradiation .products are usually ones which are known to be sensitizers in other azide systems in which coupling takes no part. The structures of the dyes obtained in the present invention appear to contain the fragment:

in which W has the same significance as in the general formula for the heterocyclic couplers. Inspection of this structure shows that the colored compounds can be considered to be related to the merocyanines. The absorption spectra of these dyes are frequently shifted by changing the solvent, a phenomenon well known in the field of merocyanine dyes. This shift in absorption due to the solvent is useful in obtaining dyes that absorb in a particular desired range. The inclusion of substituents in the azide or the heterocyclic coupler frequently causes shifts in the dye spectra, so that by a suitable combination of reactants, dyes that range in color from yellow to blue may be obtained.

The azides and heterocyclic couplers employed in the present invention and methods by which these compounds may be prepared are described in the literature. The azido compounds, for example, may be prepared by the methods described in Chem. Revs., 54, No. 1, (February, 1954). See also J. Am. Chem. Soc., 76, 1859' (1954). The coupler compounds, for example, may be synthesized by the methods described by Van Allan, Reynolds and Adel, J. Org. Chem., 27, 1659, (1962).

It will be apparent from the foregoing description that the present invention provides an advantageous method and materials for photographic reproduction of graphic material and that due to the highly colored compounds formed by the reaction of the azide irradiation products and the heterocyclic couplers the reproductions or printout images obtained have improved contrast whencompared with the reproductions produced by certain other azide-sensitized systems. The embodiments of the invention in which the print-out images can be stabilized by heat treatment or by washing out the salt of a basic ammonia derivative with warm water or dilute acid are, of course, especially advantageous where it is desired to preserve the print for extended periods of time. A considerable economic advantage is also provided by the new materials in which the light-sensitive compositions are incorporated directly in the support material due to the elimination of one of the usual coating operations.

It should be understood that the specific embodiments of the invention described above are merely illustrative and are not intended to limit the scope of the appended claims.

We claim:

1. A (light-sensitive photographic element containing:

(1) 'an organic colloidal binder;

(2) at least one light-sensitive organic azi-de selected from the class consisting of those having the formulas:

(I) ArN (I) Al( ]-N3 (III) H ArCH=CI-I-CN (IV) N\ i; J Q.

WI I

Z N \l/ N:

(VI) N N R I j N N/ Na and (VII) i t N I N wherein Ar represents an aryl group; Q represents a group from the class consisting of the oxygen atom, the sulfur .atom, the selenium atom, and a NR group; R represents a group selected from the class consisting of the hydrogen atom, an alkyl group, an aryl group, an alkytlsulfonyl group, an aryls-ulfonyl (group, an alkoxy group, an laroyl group, a carbailkoxy group, and a carbarn'yl group; R and R each represents a group selected from the class consisting of the hydrogen atom, an alkyl group, an alkoxy group, .an aryl group, the nitro group, a halogen atom, and the nonmetallic atoms such that when the R and R groups are attached to adjacent carbon atoms in the benzene ring and the said R and R groups taken together with said carbon atoms in the henzene ring complete a fused cyclic ring; R represents a 1 .group selected from the class consisting of the azide group, and an alkyl group; R represents a tgroup' selected from the class consisting of the azide group, an alkyl group, and an amino group; Z represents a group selected from the class consisting of the CH group and the nitrogen atom; and R represents a group selected from the 13 class consisting of the hydrogen atom and :an alkyl group; and

(3) at least one coupler compound selected from those having the formulas:

wherein R and R each represents a group selected from the class consisting of the hydrogen atom, .an alkyl group, and an aryl group; R and R each represents a group selected from the class consisting of the hydrogen atom, an alkyl group, an alkoxy group, an aryl group, the nitro group, a halogen atom and the nonmetallic atoms such that when the R and R groups :are attached to adjacent carbon atoms in the benzene ring, and the said R and R groups taken together with said carbon atoms in the benzene ring, the said nonmetallic atoms complete a fused cyclic ring; R and R each represents a group selected from the class consisting of the hydrogen atom, an alkyl group, an alkoxy group, an aryl group, the nitro group, a halogen atom, the hydroxy group, the oxygen atom, and the nonmetallic atoms such that when R and R are attached to adjacent carbon atoms in the benzene ring, and the said R and R groups taken together with said carbon atoms in the benzene ring, the said nonmetallic atoms complete a fused cyclic ring; and such that when R represents the oxygen atom, R also represents the oxygen atom and said oxygen atoms are attached to the nucleus through double bonds; W represents a group selected from the class consisting of the sulfur atom, the selenium atom, the oxygen atom, the S R X group, the NR group, and the CH group; R represents .an alkyl group; X represents an acid anion; R represents a group selected from the class consisting of the hydrogen atom, and an alkyl group; and n represents an integer of from 1 to 2; such that at least one of the positions on a benzene ring ortho and para to .an imino group of said coupler compound is unsubstituted.

2. A light-sensitive photographic element of claim 1 in which the said light sensitive organic azide and the said coupler compound are incorporated together with the said organic colloid binder in a self-supporting layer.

3. A light-sensitive photographic element of claim 1 in which the said light-sensitive organic azide and the said coupler compound are incorporated together with said organic colloid binder and coated in a layer on a support.

4. A light-sensitive photographic element of claim 1 containing additionally a salt of a basic ammonia derivative.

5. A light-sensitive element of claim 1 in which th organic colloid binder is an organic high polymer selected from the class consisting of gelatin; casein; rubber; cellulose acetate; a copolymer of cellulose acetate and cellulose propionate; polystyrene; poly(vinyl alcohol); poly- (vinyl butal); and copolymers of vinyl chloride and vinyl acetate.

6. A light-sensitive element of claim 1 in which the organic colloid binder is an organic high polymer selected from the class consisting of gelatin; casein; rubber; cellulose acetate; a copolymer of cellulose acetate and cellulose propionate; polystyrene; poly(vinyl alcohol); poly- (vinyl butal); and copolymers of vinyl chloride and vinyl acetate; the organic azide has Formula IV and the coupler has Formula IX.

7. A light-sensitive photographic element comprising a photographic support coated with a light-sensitive composition comprising:

(1) at least one organic high polymer selected from the class consisting of gelatin; casein; rubber; cellulose acetate; a copolymer of cellulose acetate and cellulose propionate; polystyrene; poly(vinyl alcohol); poly(vinyl *butal); and copolymers of vinyl chloride and vinyl acetate;

(2) 2-azidobenzoxazole; and

(3) benzo [a] phenothiazine.

8. A light-sensitive photographic element comprising a photographic support coated with a light-sensitive composition comprising:

(1) at least one organic high polymer selected from the class consisting of gelatin; casein; rubber; cellulose acetate; a copolymer of cellulose acetate and cellulose propionate; polystyrene; poly(vinyl alcohol); poly(vinyl 'butal); and copolymers of vinyl chloride and vinyl acetate;

(2) 2-azido-l-carbobutoxymethy-lcarbamylbenzimidazole; and

(3) benzo[-b]phenoxazine.

9. A light-sensitive photographic element comprising a photographic support coated with a light-sensitive composition comprising:

(l) at least one organic high polymer selected from the class consisting of gelatin; casein; rubber; cellulose acetate; a copolymer of cellulose acetate and cellulose propionate; polystyrene; poly(vinyl alcohol); poly(vinyl butal); and copolymers of vinyl chloride and vinyl acetate;

(2) 2-azido-1-phenylcarbamylbenzimidazole; and

(3) benzo[b]phen0xazine.

10. A light-sensitive photographic element comprising a photographic support coated with a light-sensitive com- 45 position comprising:

(1) at least one organic high polymer selected from the class consisting of gelatin; casein; rubber; cellulose acetate; a copolymer of cellulose acetate and cellulose propionate; polystyrene; poly(vinyl alcohol); poly(vinyl butal); and copolymers of vinyl chloride and vinyl acetate; (2) 2-azido-1-carboisobutoxymethylcarbamylbenzimidazole; and (3) benzo[b]phenox-azine.

11. A light-sensitive photographic element comprising a photographic support coated with a light-sensitive composition comprising:

(l) at least one organic high polymer selected from the class consisting of gelatin; casein; rubber; cellulose acetate; a copolymer of cellulose acetate and cellulose propionate; polystyrene; poly(vinyl alcohol); poly(vinyl butal); and copolymers of vinyl chloride and vinyl acetate;

from the class consisting of those having the formulas: (I) Ar-N (H) II AI-C''N3 ArOH=CHC JH (IV) N\ V N R W R Z N \l/ (VI) N N R l J N l N/ a and (VII) I I NN wherein Ar represents an aryl group; Q represents a group selected from the class consisting of the oxygen atom, the sulfur atom, the selenium atom, and a NR group; R represents a group selected from the class consisting of the hydrogen atom, an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxy group, an aroyl group, a carbalkoxy group, and a carbamyl group; R and R each represents a group selected from the class consisting of the hydrogen atom, an alkyl group, an alkoxy group, an aryl group, the nitro group, a halogen atom, and the nonmetallic atoms such that when the R and R groups are attached to adjacent carbon atoms in the benzene ring and the said R and R groups taken together with said carbon atoms in the benzene ring complete a fused cyclic ring; R represents a group selected from the class consisting of the azide group, and an alkyl group; R represents a group selected from the class consisting of the azide group, an alkyl group, and an amina group; Z represents a group selected from the class consisting of the CH group and the nitrogen atom; and R represents a group selected from the class consisting of the hydrogen atom and an alkyl group; and

(3) at least one coupler compound selected from those having the formulas:

(VIII) and I 4 R o R n wherein R and R each represents a group selected from the class consisting of the hydrogen atom, an alkyl group, and an aryl group; R and R each represents a group selected from the class consisting of the hydrogen atom, an alkyl group, an alkoxy group, an aryl group, the nitro group, a halogen atom and the nonmetallic atoms such that when the R and R groups are attached to adjacent carbon atoms in the benzene ring, and the said R and R groups taken together with said carbon atoms in the benzene ring, the said nonmetallic atoms complete a fused cyclic ring; R and R each represents a group selected from the class consisting of the hydrogen atom, an alkyl group, an alkoxy group, an aryl group, the nitro group, a halogen atom, the hydroxy group, the oxygen atom, and the nonmetallic atoms such that when R and R are attached to adjacent carbon atoms in the benzene ring, and the said R and R groups taken together with said carbon atoms in the benzene ring, the said nonmetallic atoms complete a fused cyclic ring; and such that when R represents the oxygen atom, R also represents the oxygen atom and said oxygen atoms are attached to the nucleus through double bonds; W represents 'a group selected from the class consisting of the sulfur atom, the selenium atom, the oxygen atom, the S R X group, the NR group, and the CH group; R represents an alkyl group; X represents an acid anion; R represents a group selected from the class consisting of the hydrogen atom, and an alkyl group; and n represents an integer of from 1 to 2; such that at least one of the positions on a benzene ring ortho and para to an imino group of said coupler compound is unsubstituted.

13. A light-sensitive photographic element of claim 7 containing additionally 2-azido-l-phenylcarbamylbenzimidazole and phenothiazine in the light-sensitive composition.

14. A light-sensitive photographic element of claim 8 containing additionally 2-azido-l-phenylcarbamylbenzimd azole in the light-sensitive composition.

15. A light-sensitive photographic element of claim 9 containing additionally phenothiazine in the light-sensitive composition.

16. A light-sensitive photo-graphic element of claim 10 containing additionally 2-azido-IphenyIcarbamylbenzimidazole in the light-sensitive composition.

17. A process of claim 12 in which the print-out image formed is stabilized by heating the said element to a temperature of from about C. to about C.

References Cited by the Examiner UNITED STATES PATENTS 2,844,465 7/1958 Chalkley 96-90 X 3,061,435 10/1962 Tomanek et al 9691 2,062,650 11/1962 Sagura et al. 96-91 3,099,559 7/1963 Ooles 96-90 X NORMAN G. TORCHIN, Primary Examiner.

R. L. STONE, A. D, RICCI, Assistant Examiners,

(5/69) UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent 3.282.693 LNovember 1 1Q66 Inventor(s) John J. Sagura and James A. VanAllan It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

j Column 2, line 56, between the words "group" and "from" insert -selected-- Column 1 5, line EL; (1 9th line under structural formula VII), delete "amina" and substitute in its place --amino-.

ulbNLU Am.) SEALED IEZSW (SEAL) Attest:

Edward M. Fletcher, Jr. W

ILLIAM E. souuYLER, JR. Attesung Offlcer Commissioner of Patents 

12. A PROCESS FOR FORMING A PRINTOUT IMAGE IN A LIGHTSENSITIVE PHOTOGRAPHIC ELEMENT COMPRISING THE STEP OF EXPOSING THE LIGHT-SENSITIVE LAYER OF SAID ELEMENT TO ACTIVATING RADIATION THROUGH AN ORIGINAL IMAGE, SAID ELEMENT HAVING A LIGHT-SENSITIVE LAYER CONTAINING: (1) AN ORGANIC LIGHT-SENSITIVE ORGANIC AZIDE SELECTED (2) AT LEAST ONE LIGHT-SENSITIVE ORGANIC AZIDE SELECTED FROM THE CLASS CONSISTING OF THOSE HAVING THE FORMULAS:
 17. A PROCESS OF CLAIM 12 IN WHICH THE PRINT-OUT IMAGE FORMED IS STABILIZED BY HEATING THE SAID ELEMENT TO A TEMPERATURE OF FROM ABOUT 75* C. TO ABOUT 150* C. 